Process for breaking petroleum emulsions employing certain amine-modified thermoplastic phenol-aldehyde resin salts



United States Patent 2,771,44i Patented Nov. 20, 1956 time PROCESS FOR BREAKING PETROLEUM EMUL- SIONS EMPLOYING CERTAIN AMlNE-MODI- FIED THERMOPLASTIC PHENOL-ALDEHYDE RESIN SALTS Melvin De Groote, University City, Mo., assignor to Petrolite Corporation, Wilmington, Del., a corporation of Delaware No Drawing. Application January 2, 1953, Serial No. 329,483

18 Claims. (Cl. 252-341) The present invention is a continuation-in-part of my two co-pending applications, Serial No. 288,743, filed May 19, 1952, now abandoned, and Serial No. 296,084, filed June 27, 1952, now U. S. Patent 2,679,485.

My invention provides an economical and rapid process for resolving petroleum emulsions of the water-in-oil type, that are commonly referred to as cut oil, roily oil, emulsified oil, etc., and which comprise fine droplets of naturally-occurring waters or brines dispersed in a more or less permanent state throughout the oil which constitutes the continuous phase of the emulsion.

It also provides an economical and rapid process for separating emulsions which have been prepared under controlled conditions from mineral oil, such as crude oil and relatively soft waters or weak brines. Controlled emulsification and subsequent demulsification under the conditions just mentioned are of significant value in removing impurities, particularly inorganic salts, from pipeline oil.

My aforementioned co-pending application, Serial No. 296,084, filed June 27, 1952, is concerned with a process for breaking petroleum emulsions of the water-in-oil type characterized by subjecting the emulsion to the action of a demulsifier including certain condensates of basic hydroxylated secondary monoamines with certain phenolaldehyde resins and formaldehyde described therein.

My present invention is concerned with demulsification which involves the use of the aforementioned amino resin condensate in the form of a gluconic acid salt, i. e., a form in which all or part of the basic nitrogen atoms are neutralized with gluconic acid which, for practical purposes, is as simple as analogous inorganic reactions.

As far as the use of the herein described products go for purpose of resolution of petroleum emulsions of the water-in-oil type, I particularly prefer to use the gluconic acid salt of those members which have sufficient hydrophile character to meet at least the test set forth in U. S. Patent No. 2,499,368, dated March 7, 1950, to De Groote et al. In said patent such test for emulsification using a water-insoluble solvent, generally xylene, is described as an index of surface activity.

The present invention involves the surface-activity of the gluconic acid salts, i. e., either where only one basic amino nitrogen atom is neutralized or where all or part of basic amino nitrogen atoms are neutralized. Such gluconic acid salts may not necessarily be xylene-soluble. If such compounds are not xylene-soluble the obvious chemical equivalent or equivalent chemical test can be made by simply using some suitable solvent, preferably a water-soluble solvent such as ethylene glycol diethylether, or a low molal alcohol, or a mixture to dissolve the appropriate product being examined and then mix with the equal weight of xylene, followed by addition of water. Such test is obviously the same for the reason that there will be two phases on vigorous shaking and surface activity makes its presence manifest. It is understood the reference in the hereto appended claims as described in applications Serial Nos. 288,743 and 296,084,

of .the radical R, there may be a counter-balancing hydro to the use of xylene in the emulsification test includes such obvious variant.

For convenience, what is said hereinafter will be divided into six parts:

Part 1 is concerned with the general structure of the amine-modified resins which are converted into the gluconto acid salt;

Part 2 is concerned with the phenol-aldehyde resin which is subjected to modification by condensation reaction to yield the amine-modified resin;

Part 3 is concerned with appropriate basic secondary hydroxylated amines which may be employed in the prepara-' tion of the herein described amine-modified resins;

Part 4 is concerned with the reactions involving the resin, the amine, and formaldehyde to produce the specific PART 1 The compounds herein described and particularly useful as demulsifying agents are gluconic acid salts of heatstable oxyalkylation-susceptible resinous condensation products of certain basic hydroxylated secondary monoamines, certain phenol-aldehyde resins and formaldehyde to which reference is made for a discussion of the general structure of such resins.

These resins may be exemplified by an idealized formula which may, in part, be an over-simplification in an effort to present certain resin structure. Such formula would be the following:

a R n R in which R represents an aliphatic hydrocarbon substituent generally having four and not over 18 carbon atoms but most preferably not over 14 carbon atoms, and n generally is a small whole number varying from 1 to 4. In the resin structure it is shown as being derived from formaldehyde although obviously other aldehydes are equally satisfactory. The amine residue in the above structure is derived from a basic amine, and usually a strongly basic amine, and may be indicated thus:

RI HN for instance, one having 3 to 6 phenolic nuclei as specified,-

alters the resultant product in a number of ways. Inthe first place, a basic nitrogen atom, of course, adds a hydro phile effect; in the second place, depending on thesize phobe effect or one in which the hydrophobe effect more than counterbalances the hydrophile effect of the nitrogen atom. The presence of one or more hydroxyl radicals introduces a significant hydrophile effect. Finally, in such cases where R contains one or more oxygen atoms in the form of an ether linkage another effect is introduced, particularly another hydrophile effect.

The resins employed as raw materials in the instant procedure are characterized by the presence of an aliphatic radical in the ortho or para position, i. e., the phenols themselves are difunctional phenols.

The .resinsherein employed contain only two terminal groups which arercactive to formaldehyde, i. e., they are difunctional from the standpoint of methylol-forming re actions. Asis'well known, although one may start'with difunetional phenols, and depending on the procedure employed,:one'may obtain cross-linking which indicates that one ormore of the phenolic nuclei have been converted from a difunctional radical'to a trifunctional radical, or in terms of theresin,the molecule as a whole has a methylolforming reactivity greater than 2. Such shift can take place after" the resin has beenform'ed or during resin formation. Briefly, an example is simply where an alkyl radical,-such as methyl, ethyl, propyl, butyl, or the like, shifts-froman ortho position to a meta position, or from a para .position toa meta position. For instance in. the case of phenol-aldehyde varnish resins, one can prepare at least some in which the resins, instead of having only two points of reaction can have three, and possibly more points of:reaction, with formaldehyde, or any other reactantlwhich tends to'form a methylol or substituted methylol group.

The resins herein employed are soluble in a nonoxygenated hydrocarbon solvent, such as benzene or xylene. The resins herein employed as raw materials must be comparatively low molal products having on the average 3 to 6 nuclei per resin molecule.

The condensation products here obtained, whether in the form of the free base or the salt, do not go over to the insoluble stage on heating. The condensation product obtained according to the present invention is. heat stable and, in fact, one of its outstanding qualities is that it can be subjected tooxyalkylation, particular oxyethylation or oxypropylatiion, under conventional conditions, i. e., presence of an alkaline catalyst, for example, but in any event at a temperature above 100 C. without becoming an insoluble mass.

What has been said previously in regard to heat stability,

particularly whenemployed as a reactant for preparation of derivativegisstill important from the standpoint of manufacture of the condensation products themselves in sidf'afthat in the condensation: process employed in preparing the'compou'nds described subsequently in detail,

thr'eis no objection 'to the employing of a temperature.

above the boiling point of water. As a matter of fact, all the examples included subsequently employ, temperatures going up to 140 to 150CQ What is said above deserves further amplification at this point for the reason that it may shorten what is said subsequently in regard to the production of the herein described condensation products. Since formaldehyde generally is employed economically in an aqueous phase 30% to 49% solution, for example) it is necessary to have manufacturing procedure which will allow reactions to take'pla'ceat the interface of the two immiscible liquids, to yvit the'formaldehyde solution and the resin solution, o'n-the assumption that generally the amine will dissolve in one phase or the other. Although reactions of the kind'herein described will begin at least at comparatively low' temperatures, for instance, 30 C., 40 C., or 50 0., yet the reaction does'not go to completion except by the use of the higher temperatures. The use of higher temperatures means, of course, thatthe condensation product obtained at the end of the reaction must not be heat reactive. Of course, one can add an oxygenated solvent suchas alcohol, dioxane, various ethers of glycol's, or the like, and produce a homogeneous phase. If this latter procedure is employed in preparing the herein described condensations it is purely a matter of convenience, but whether it is or not, ultimately the temperature must still pass within the zone indicated elsewhere, i. e., somewhere above the boiling point of water unless some obvious equivalent procedure is used.

Any reference, as in the hereto appended claims, to the. procedure employed in the process is not intended'to limit the method or order in which the reactants are added, commingled or reacted. The procedure has been referred to as a condensation process for obvious reasons. As pointed out elsewhere it is my preference to dissolve the resin in a suitable solvent, add the amine, and then add the formaldehyde as a 37% solution. However, all three reactants can be added in any order. I am inclined to believe that in the presence of a basic catalyst, such as the amine employed, that the formaldehyde produces methylol groups attached to the phenolic nuclei, which, in:,turn, react with the amine was to introduce a methylol group attached to nitrogen which, in turn, would react with the resin molecule. Also, it would be immaterial if; both types of compounds were formed which reactedwith'each other with the evolution'of a mole of formaldehyde available for further reaction. Furthermore, a reaction could take place in which three different molecules are simultaneously involved although, for theoretical reasons, that is lesslikely. What is said herein in this respect is simply. by way of explanation to avoid any limitation in regard to the appended claims.

PART '2 It is well known that one can readily purchase on the open market, or prepare fusible, organic solvent-soluble, water-insoluble resin polymers of a composition approximated inan idealized form by the formula R n R In; the aboye formula-n represents a small whole nurnber varying-frorn l to 6, 7 or 8, ormore, upto probably l0 'orl2 un it s, particularly when the -resin;is subjected to heating under-a-vacuum as described in the literature. A limited. sub-genus is in-the instance of low molecular weightpolymers where the total number of phenol nuclei varies from 3 m6, i. e., n-varies from, 1 to 4',R represents an aliphatic hydrocarbon substituent, generally an alkylradical having from 4 to 14 carbon atoms, such asabuty-LamyLhexyl, decyl or dodecyl radical. Where the divalent bridge radical is shown as being derived from formaldehydeit may, of course, be .derived from any other, reactive aldehyde having 8 carbon atoms or less.

Theresins -herein employed as raw materials must be soluble; in a nonoxygenated solvent, such as benzene or xylene. Thispresents-noproblem insofar/that: allthat is required is to make a solubility test on commercially available resins,- o r else prepare resins which are xylene or benzene-soluble as described in aforementioned U. S. PatentNo. 2,499,365, or in U. S. Patent No. 2,499,368 dated March7, 1950 to De Groote and Keiser.

If one selected a resin of thekind just described previously and reacted-approximately one mole of the resin with two moles of formaldehyde and .two moles of .a basic l-non-hydroxylated secondary amine asspecified, following-the same idealized over-simplification previously referred to, the resultant product might be illustrated The basic hydroxylated amine may be designated thus:

RI HN In conducting reactions of this kind one does not necessarily obtain a hundred percent yield for obvious reasons. Certain side reactions may take place. For instance, 2 moles of amine may combine with one mole of the aldehyde or only one mole of the amine may combine with the resin molecule, or even to a very slight extent, if at all, 2 resin units may combine without any amine in the reaction product, as indicated in the following formulas:

As has been pointed out previously, as far as the resin unit goes one can use a mole of aldehyde other than formaldehyde, such as acetaldehyde, propionaldehyde or butyraldehyde. The resin unit may be ememplified thus OH OH "I OH URIHURIII R R 71 R in which R' is the divalent radical obtained from the particular aldehyde employed to form the resin. For reasons which are obvious the condensation product obtained appears to be described best in terms of the method of manufacture.

As previously stated the preparation of resins, the kind herein employed as reactants, is well known. See previously mentioned U. S. Patent 2,499,368. Resins can be made using an acid catalyst or basic catalyst or a catalyst having neither acid or nor basic properties in the ordinary sense or without any catalyst at all. It is preferable that the resins employed be substantially neutral. In other words, if prepared by using a strong acid as a catalyst, such strong acid should be neutralized. Similarly, if a strong base is used as a catalyst it is preferable that the base be neutralized although I have found that sometimes the reaction described proceeded more rapidly in the presence of a small amount of a free base. The amount may be as small as a 200th of a percent and as much as a few ths of a percent. Sometimes moderate increase in caustic soda and caustic potash may be used. However, the most desirable procedure in practically every case is to have the resin neutral.

In preparing resins one does not get a single polymer, i. e., one having just 3 units, or just 4 units, or just 5 units, or just 6 units, etc. It is usually a mixture; for instance, one approximating 4 phenolic nuclei will have some trimer and pentamer present. Thus, the molecular weight may be such that it corresponds to a fractional value for n as, for example, 3.5, 4.5 or 5.2.

In the actual manufacture of the resins I found no reason for using other than those which are lowest in price and most readily available commercially. For purposes of convenience suitable resins are characterized the following table:

TABLE I M01. wt. Ex- R of resin ample R Position derived n molecule number of R from- (based Phenyl Para. Formal- 3. 5 992. 5

dehyde. Tertiary butyl do do 3. 5 882. 5 Secondary butyl. Ortho... 3. 5 882. 5 yfi p-hexyl Para. 3. 5 1, 025. 5 Tertiary amy1 lo... 3. 5 959. 5 Mixed secondary Ortho... 3. 5 805. 5

and tertiary amyl. Propyl 3. 5 805. 5 Tertiary hexy 3. 5 1, 036. 5 Oetyl. 3. 5 1, 190. 5 N onyL 3. 5 1, 267. 5 Deeyl. 3. 5 1, 344. 5 Dodecy 3. 5 1, 498. 5 Tertiary butyl 3. 5 945. 5

Tertiary amyl 3. 5 1, 022. 5 15a Nonyl 3. 5 1, 330. 5 16a Tertiary butyl 3. 5 1, 071. 5

Tertiary amyl 3. 5 1, 148. 5 Nonyl 3. 5 1, 456. 5 Tertiary butyl Propion- 3. 5 1, 008. 5

aldehyde.

4. 2 1, 083. 4 onyl 4. 2 1, 430. 6 Tertiary butyL 4. 8 1, 094. 4 Tertiary amyl 4. 8 1, 189. 6 4. 8 1, 570. 4 1. 5 604. 0 1. 5 646. 0 l. 5 653. 0 1. 5 688.0

2. 0 692. 0 yl 2. 0 748. 0 40a Oyclo-hexyl do 2. 0 740. 0

PART 3 As has been pointed out previously the amine herein employed as a reactant is a basic hydroxylated secondary monoamine whose composition is indicated thus:

R! in which R represents a monovalent alkyl, alicyclic, arylalkyl radical which may be heterocyclic in a few instances as in a secondary amine derived from furfurylamine by reaction of ethylene oxide or propylene oxide. Furthermore, at least one of the radicals designated by R must have at least one hydroxyl radical. A large number of secondary amines are available and may be suitably employed as reactants for the present purpose. Among others, one may employ diethanolamine, mefihyl ethanolamine, dipropanolamine and ethylpropanolamine. Other suitable secondary amines are obtained, of course, by tak; ing any suitable primary amine, such as an alkylamine, an arylalkylamine, or an alicyclic amine, and treating the amine with one mole of an oxyalkylating agent, such as ethylene oxide, propylene oxide, butylene oxide, glycide, or methylglycide. Suitable primary amines which can be so converted into secondary amines, include butylamine, arnylamine, hexylamine, higher molecular weight amines derived from fatty acids, cyclohexylamine, benzylamine, furfurylamine, etc. In other instances secondary amines which have at least one hydroxyl radical can be treated similarly with an oxyalkylating agent, or, for that matter, with an :alkylating agent such as benzylchloride, esters of chloroacetic acid, alkyl bromides, dimethylsulfate, esters of sulfonic acid, etc., so as to convert the amino-2-ethyl-l,3-propanediol, and tris-(hydroxymethyly aminomethane. Another example of such amines is illustra-ted by 4-amino-4-methyl-2-pentanol.

Similarly, one. can prepare suitable secondary amines which have not only a hydroxyl group but also one or more divalent oxygen link-ages as part of an ether radical. The preparation of such amines or suitable reactants for preparing them has been described in the literature and particularly in two United States patents, to wit, U. S. Patents Nos. 2,325,514, dated July 27, 1943, to Hester, and 2,355,337 dated August 8, 1944 to Spence. The latter patent describes typical haloalkyl others such as CHaOCzHiCl CHr-CH:

OH; 011-01120 C2H4O C2H4Br CgHEOCZHAOC2H40CZ 4OC2H4C1 Such haloalkyl ethers can be reacted with ammonia or with a primary amine, such as ethanolamine, propanolamine, monoglycerylamine, etc., to produce a secondary amine in which there is not only present a hydroxyl radical but a repetitious ether linkage. Compounds can be readily obtained which are exemplified by the following formulas:

(C2H50 02 40 C2114) HO C 114 (CBHITO CzHtO CzH4O CzHt) HOC2H4 (CHsO CHzCHzO CHaCHzO C'HzCHz) HO C2114 (CHaO CHzCHgCHzCHgCHzCHg) HOC2H4/ or comparable compounds having two hydroxylated groups of different lengths as in (HOCHzCHzOCHzCHzOCHzCHz) Other examples of suitable amines include alpha-methylbenzylamine and monoethanolamine; also amines obtained by treating cyclohexylmethylamine with one mole of an oxyalkylating agent as previously described; beta-ethylhexyl-butanolamine, diglycerylamine, etc. Another type of amine, which is of particular interest because it includes a verydefinite hydrophile group includes sugar amines such as glucamine, gelactamine and fructamine, such as N-hydroxyethylglucamine, N-hydroxyethylgalactamine, and. N-hydroxyethylfructamine.

. Other suitable amines may be illustrated by CH3 HO.CH2.( J.CH2OH NH HO.CHz.( J.CH2OH CH3 CH3 CH3.C.CH2OH Clix-( 1.0112011 3H3 See, also, corresponding hydroxylated amines. which, can be obtained from rosin or similar raw materials and described in U. S. Patent No. 2,510,063, dated June 6, 1950, to Bried. Still other examples are illustrated by treatment of certain secondary amines, such as the following, with a mole of an oxyalkylating agent as described;

phenoxyethylamine, phenoxypropylamine, phenoxyalphamethylethylamine, and phenoxypropylamine.

Other procedures for production of suitable compounds having a hydroxyl group and a single basic amino nitro gen atom can be obtained from any suitable alcohol or.

the like by reaction with a reagent which contains an epoxide group and a secondary amine group. Such re-., actants are described, for example, in U. S. Patents Nos PART 4 The products obtained by the herein described processes represent cogeneric mixtures which are the result of a condensation reaction or reactions. Since the resin molecule cannot be defined satisfactorily by formula, although it maybe so illustrated in an idealized simplification, it is difficult to actually depict the final product of the cogeneric mixture except in terms of the process itself. The condensation of the resin, the amine and formaldehyde is described in detail in applications Serial Nos.

288,743 and 296,084, and reference is made to those 1 applications for a discussion of. the factors involved.

Little more need be said as to the actual procedure employed for the, preparation of the. herein described condensation products. The following example will serve by way of illustration:

Example 111 The phenol-aldehyde resin is the one that has been identified previously as Example 20. It was obtained from a para-tertiary butylphenol and formaldehyde. The resin was prepared using an acid catalyst which was completely neutralized atv the end of the reaction. The. molecular weight of the resin was 882.5. This corresponded to an average of about 3 /2 phenolic nuclei, as the value for n which excludes the 2 external nuclei, i. e., the resin was. largely a mixture having 3 nuclei and 4 nuclei, excluding the 2 external nuclei, or 5 and 6 overall nuclei. The resin so obtained in a neutral. state had a light amber color.

882 grams of the resin identified as 2a preceding were powdered and mixed with 700 grams of xylene. The mixture was refluxedw until solution was complete. It was then adjustedto approximately 30 to 35 C. and 210. grams of diethanolamine added. The mixture was stirred vigorously and. formaldehyde added slowly. The formaldehyde used was a 37% solution and grams were employed which were added in about 3 hours. The mixture was stirred vigorously and kept within a temperature rangeof 30 to 45 C. for about 21 hours. At the end of this period of timeit was refluxed, using a phaseseparating trap and a small amount of aqueous distillate. withdrawn from time to time and the presence of unreacted formaldehyde noted. Any unreacted formaldehyde seemed to disappear within approximately 3 hours after the refluxing was started. As soon as the odor of formaldehyde was no longer detectible the phase-separating trap was set so as to eliminate all water of solution and reaction. After the water was eliminated part of the xylene was removed until the temperature reached about 150 C. The mass was kept at this higher temperature for about 3% hours and reaction stopped. During this time any additional water, which was probably water of reaction which had formed, was eliminated by means of 5 the trap. The residual xylene was permitted to stay in A small amount of the sample was heated on a water bath to remove the excess xylene and the residual material was dark red in color and had the consistency of a sticky fluid or a tacky resin. The 10 overall reaction time was a little over 30 hours. instances it has varied from approximately 24 to 36 hours. The time can be reduced by cutting the low temperature period to about 3 to 6 hours.

the cogeneric mixture.

In other illustrated by 24 examples in Table II.

In eachcase the initial mixture was stirred and held at'it fairly low temperature (30 'to 40 C.) for a period'of several hours. Then refluxing was employed until the odor of formaldehyde disappeared. Aftertheod'o'r'of formaldehyde disappeared the phase-separating trap was employed to separate out all the water, both the solution and condensation. After all the water had been separated enough xylene was taken out to have the final product reflux for several hours somewhere in therange of 145 to 150 C., or thereabouts. Usually the mixture yielded a clear solution by the time the bulk of the water, or all of the water, had been removed.

Note that as pointed out previously, this procedure is Note that in Table H following there are a large number of added examples illustrating the same procedure.

TABLE II Strength of Reac- ,Reac- Max. Ex. Resin Amt, Amine used and amount iormalde- Solvent used tion tlon distill. N0, used hyde soln. and amt. temn, time tern and amt. (hrs) 1b..... 2a..." 882 Diethanolamjne, 210 g 37%, 162 3- Xylene, 700 g.... 22-26 32 131 2b 5a-.-" 480 Diethanolamine, 105 g 37%, 81 g-- Xylene, 450 g 21-23 28 150 3b 10a 633 do .do Xylene, 60015.... 7 20-22 .36 145 4b..-" 241"--. 441 Dipropanolamine, 133 g 100 g-- Xylene, g 20-23 34 146 5b 5a- 480 dn do Xylene, 450 gm. 21-23 v24 141 6b--- a 633 do y 60 g- 21-28 24 145 7b 2a 882 Ethylethanolamine, 178 g 162 g--- Xylene, 700 g-. 20-26 24 152 8 5a--." 480 Ethylethanolamine, 89 g 3 81 g-- Xyl 450 E 24-30 28' 151 9b 10/: 633 do 1 1 do .Xylene, 600 gm- 22-25 27 147 1011--.- 130-..- 473 Cyclohexylethanolamine, 143 g.-- 100 g- Xyl 4 g 21-31 31 146 11b- 1411---- 511 do 37%, 81 g Xylene, 450 g 22-23 36 148 1%.... a 665 (in do Xylene, 550 gm- -24 27 152 135..-- 2a-. 441 02115005400111; Xylene, 400 2.... 21-25 24 150 NH, 176 g.

HOCaHA 1412...- 5a. 480 mmocinocini 1 Xylene, 50 gm. 20-26 26 146 NH, 176 g.

HOCzHt 151)---- 9a--- 595 CjHiOCflHOCZH; d0 Xylene, 550 g 7 21-27 80 147 HOCaHt 161)---. 2a-- 441 HOCgH4OOQH4OC2H4 ""1 0 Xylene, 400 gn 20-22 30 148 HOCgH;

1717---- 5a.-- 480 HOC=H OC H OGH4 d0 20-25 28 150 NH, 192 g.

HOC H;

1%.... 1411.... 591 H0C2H4OC2H4OO:H4 do Xyle e, 500 2 32 149 NH, 192 g.

HOCZHA 190---. 22a 498 HOCZHLOC1H4002H4 y 450 g- 22-25 32 153 NH, 192 g.

HOCQH4 20b 23a 542 CHa(OC2H4)s 3Q%, 100 g. Xylene, 500 g---- 21-23 36 151 HOC2H4 21b a 547 0114002114); -do -do 25-30 34 143 NH, 206 g.

HOC1H4 220--.- 2a- 441 CH;(OC H4)3 do Xylene, 400 g-, 22-23 31 146 HOC2H4 260.-.- 595 Decylethanolamine, 201 g 81 g Xylene, 500 22-27 24 145 2711.- 391 Deeylethanolamine, 100 g g-- Xylene, 300 gm. 21-25 26 147 PART 5 The conversion of the basic condensates of the kind previously described into the corresponding salt of gluconic acid is a simple operation since it is nothing more 1 1 norless. than neutralization. The condensates. invariably contain more. than two basic nitrogen, atoms. .Oiie can neutralize eitherone, or both,basienitrogematomst; I Gluconicacidis available. as; a 50% sli1tion..Dehy

at all. times. is left "below 140 C. At the end of the separation a suitable amountof solvent is added, or 'elinili mined concentration, for instance, 50%.

dration. causes, decomposition. This is. nottruaofnthe. 5. Usin'ga so e Similar preeedureolle fl b h l salts,. at leastnot of, the salts of the herein. described consplvenvfree materlal y merely ib qy 1: densates.v Suchsalts. appear to bestable, or stable. forfall non of the condensate to vacuum dist llatlon so'as lDI practicalpurposes, at temperatures slightly abovethe boil: remOVe all the y The condensate ltselfls P e ly. ing point of waterand perhaps. at temperaturesashigh Stable at Or thereabohts a thus, there 18 1 as 150 cnorthereabouts. 1 particular danger of degradation involved 'in this step. 'reasdns.pointed out Previously, it i mast ccnven- The solvent-free material is then dissolvedv in benzene ient to handle the condensate as a. solution, generallya Instead Of y e and Weter eliminated fhe n solution. inaninexpensive. solvent, suchas benzenerxy- P y le e q The benzene 1s um d 'hlt' lene, an aromatic petroleum-solvent,,or the like. Anum- Vacuum dlshllelleh In such a Way I mp q q ber of the condensates previously'described' have been, l5. gets aheve 4 h y, Wlth" phehatedhm 50 Solution as noted Adding the l care the solution previously described, to wit, the xylenee latedstoichiometric amount of 50% gluconic acid, calcubenzene 'sehlhefli also can be removed Wltheut latcd: on the basiszof' the theoretical basic nitrogen atoms eempeeltlehpresent, forms such'salt which, in many instances may b Broadly speaking, the glucomc: ac1d salts represent salts slightly on the basic side in. other. instances perhaps 20 P hydroxylated e y h In other W there slightly on the acid side. The Salt formation, is merely a 1s an analogy to trlethanolarmne oleate or, for that matter, matter of agitating at room temperature or somewhat tr1ethanolam1ne gluconate. If triethanolamlne gluconate higher temperature if desired, particularly under a reflux 1S heated to epproxlmately 9 there'seems m be f condenser. After salt formation is complete, I have perfiance there converslon'mto the acylate-d amme mitted the solution to stand for about 6 to 72 hours. ewghlccfnyl trlethellelamlhe, e p f the f Sometimes depending on the composition, there issome s1on of triethanolamme oleate lnto oleyl triethanolamme. Separation of an aqueous phase o a laboratory Scale, For this reason, prevlous reference to decomposition must this procedure is conducted in a separately funnel. If be construed to mean not only decomposition inthe sense there is separation of an aqueous phase, the aqueous phase F degradatlon-or ethers may be 'formedi but also is discarded and the solution can he brought back to a 111 the sensethat an entirely new and valuable compound predetermined concentration by the addition of a hydromay be formed' Such reactlon, of course forms water carbon solvent, such as xylene, or by the addition of an as a byproductalcohol, such. as methyl, ethyl or propyl alcohol; or, if Example 16 need be, one can employ a bridge solvent having hydro- Thls Salt made from Condensate hP tropic properties in case of the diethylether of ethylene- Example lb in turn was made from resin 2a and dlethanolglycoLor imila olve t amine. 882 grams of the resin dissolved in an equal The gluconic salts can be obtained in non-aqueous soluwelghfefxylene e reacted With 210 grams of methanoltion byvusing a slightly modified procedure. The proamulet and g-g 9 de yd All thls cedure depends on the fact that the phase-separating trap hisv been desel'lbed p y; The Weight of the can be: used but it is preferable to stay below 150 C. so 40 d'ensate on a solvenbfree basis w s 1 Thls as to avoid any possible decomposition. representeel PP l Y 27 grams of basic nitrogen- The xylene solution of the condensate, as previously T0 thls m1Xtl11'e;.With eonstahtl stifl'ingi there Was added described, is subjected to vacuum distillation so as to 756 grafms 0f 50% glueehle fleid- TheSOhltiOn Was remove about one-half the xylene. Approximately two- Poured Into a Separately funnel yp al'l'elhgemellt thirds of the, xylene removed is replaced by benzene. end allowed to Stand at for about 21/2 days- This mixed solvent combination is subjected to refluxing Therewasaqueous separafieh at the bettomor, at the action under a condenser with a phase-separating trap. most, e y a trace The SOhlfiOIl Was Somewhat turbid With the distillation point adjusted so as to be somewhere and for thls reason about 100 grams of P PY alcohol between 110 to 135 c. the mixture is refluxed and the e added and enough Xylene to bring the fi weight water separated. If it is not within this range more bent0 l Short of 3000 f El exactly 2988 gramszerre is added or, if need be, a little more xylene is added. Thls represented approxlmately a 50% Solutionto bring it within the range. By this method the phase- A number of other examples are included in Table III, separating trap eliminates the water. The temperature following.

TABLE III Condensate in turn derived irom Salt formation Salt Salt from Wt. 015 Final ex. con- Amt. 37% conden- Theo. 50% wt. ad- No. den- Resin Amt. sol- Amine formsate on basic glujusted to sate No. resin, Solvent vent, Amine used used, aldesolventnitroconic approx. No. gms. gms. gms. hyde, free gen, acid, salt,

gms. basis, gins. gms. 50% solv.,

gms. gms.

210 162 1, 116 27.0 756 2, 988 105 31 597 13. 5 37s 1, 572 105 81 750 13. 5 373 1, 878 133 1 586 13.6 330 1,552 133 100 625 13.0 380 1, 630 133 1 100 778 13.6 330 1, 936 178 162 1, 034 23. o 784 2, 952 0 s9 81 531 14. o 392 1, 554 533 do s9 21 734 14.0 392 1,860 473 cyclohexylethanolaminen 143 100 671 14.0 392: 1,734 511 ds ,143 -31 724. 14.0 392.. 1,848 665 do 143 81 882 14.0 392 2,156 332 Diethanolamin 210 162 1,116 27. 0 37s- 2,610 441 Dipropanolamine 133 100 586 13.5 189 1,361 882 Ethylethanolamine. 178 162 1, 084 28.0 392 2, 560

1 30% formaldehyde.

13 PART 6 Conventional demulsifying agents employed in the treatment of oil field emulsions are used as such, or after dilution with any suitable solvent, such as water, petroleum hydrocarbons, such as benzene, toluene, xylene, tar acid oil, cresol, anthracene oil, etc. Alcohols, particularly aliphatic alcohols, such as methyl alcohol, ethyl alcohol, denatured alcohol, propyl alcohol, butyl alcohol, hexyl alcohol, octyl alcohol, etc., may be employed as diluents. Miscellaneous solvents such as pine oil, carbon tetrachloride, sulfur dioxide extract obtained in the refining of petroleum, etc., may be employed as diluents. Similarly, the material or materials employed as the demulsifying agent of my process may be admixed with one or more of the solvents customarily used in connection with conventional demulsifying agents. Moreover, said material or materials may be used alone or in admixture with other suitable well-known classes of demulsifying agents.

It is well known that conventional demulsifying agents may be used in a water-soluble form, or in an oil-soluble form, or in a form exhibiting both oiland water-solubility. Sometimes they may be used in a form which exhibits relatively limited oil-solubility. However, since such reagents are frequently used in a ratio of 1 to 10,000 or 1 to 20,000, or 1 to 30,000, or even 1 to 40,000, or 1 to 50,000 as in desalting practice, such an apparent insolubility in oil and water is not significant because said reagents undoubtedly have'solubility within such concentrations. This same fact is true in regard to the material or materials employed as the demulsifying agent of my process.

In practicing the present process, the treating or demulsifying agent is used in the conventional Way, well known to the art, described, for example, in Patent 2,626,929, dated January 27, 1953, Part 3, and reference is made thereto for a description of conventional procedures of demulsifying, including batch, continuous, and down-the-hole demulsification, the process essentially involving introducing a small amount of demulsifier into a large amount of emulsion with adequate admixture with or without the application of heat, and allowing the mixture to stratify.

As noted above, the products herein described may be used not only in diluted form, but also may be used admixed with some other chemical demulsifier. A mixture which illustrates such combination is the following:

Gluconic acid salt, for example, the product of Example 1c, 20%;

A cyclohexylamine salt of a polypropylated naphthalene monosulfonic acid, 24%;

An ammonium salt of a polypropylated naphthalene monosulfonic acid, 24%;

A sodium salt of oil-soluble mahogany petroleum sulfonic acid, 12%;

A high-boiling aromatic petroleum solvent, 15%;

Isopropyl alcohol, 5%.

The above proportions are all weight percents.

Having thus described my invention what I claim as new and desire to secure by Letters Patent, is:

l. A process for breaking petroleum emulsions of the water-in-oil type characterized by subjecting the emulsion to the action of a demulsifier including the gluconic acid salts of the basic products obtained in turn in the process of condensing (a) an oxyalkylation-susceptible, fusible, non-oxygenated organic solvent-soluble, water-insoluble, low-stage, phenol-aldehyde resin having an average .molecular weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule; said resin being difunctional only in regard to methylolforming reactivity; said resin being derived by reaction between a difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and reactive toward said phenol; said resin being formed in the substantial absence of trifunctional phenols; said phenol being of the formula in which R is an aliphatic hydrocarbon radical having at least 4 and not more than 24 carbon atoms and substituted in the 2,4,6 position; (b) a basic hydroxylated secondary monoamine having not more than 32 carbon atoms in any group attached to the amino nitrogen atom, and (0) formaldehyde; said condensation reaction being conducted at a temperature sufficiently high to eliminate water and below the pyrolytic point of the reactants and resultantsv of reaction; and with the proviso that the resinous condensation product resulting from the process be heat' stable.

2. A process for breaking petroleum emulsions of the water-in-oil type characterized by subjecting the emulsion to the action of a demulsifier including the gluconic acid salts of the basic products obtained in turn in the process of condensing (a) an oxyalkylation-susceptible, fusible, non-oxygenated organic solvent-soluble, water-insoluble, low-stage phenol-aldehyde resin having an average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule; said resin being difunctional only in regard to methylol-forming reactivity; said resin being derived by reaction between a difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and reactive toward said phenol; said resin being formed in the substantial absence of trifunctional phenols; said phenol being of the formula in which R is an aliphatic hydrocarbon radical having at least 4 and not more than 24 carbon atoms and substituted in the 2,4,6 position; (b) a basic hydroxylated secondary monoamine having not more than 32 carbon atoms in any group attached to the amino nitrogen atom, and (c) formaldehyde; said condensation reaction being conducted at a temperature sufficiently high to eliminate water and below the pyrolytic point of the reactants and resultants of reaction; with the added proviso that the condensation reaction be conducted so as to produce a significant portion of the resultant in which each of the three reactants have contributed part of the ultimate molecule; and with the further proviso that the resinous condensation product resulting from the process be heatstable. 7

3. A process for breaking petroleum emulsions of the water-in-oil type characterized by subjecting the emulsion to the action of a demulsifier including the gluconic-acid salts of the basic products obtained in turn in the process of condensing (a) an oxyalkylation-susceptible, fusible, non-oxygenated organic solvent-soluble, water-insoluble, low-stage phenol-aldehyde resin having an average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule; said resin being difunctional only in regard to methylol-forming reactivity; said resin being derived by reaction between a difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and reactive toward said phenol; said resin being formed in the substantial absence of trifunctional phenols; said phenol being of the formula in which R is an aliphatic hydrocarbon radical having at least 4 and not more than 24 carbon atoms and substituted in the 2,4,6 position; (b) a basic hydroxylated secondary monoamine having not more than 32 carbon atoms in any group attached to the amino nitrogen atom, and (c) formaldehyde; said condensation reaction being conducted at a temperature sufficiently high to eliminate water and below the pyrolytic point of the reactants and resultantsof reaction, with the provisothat the condensation reaction be conducted so as to produce a significant portion of the resultant in which each of the three reactants have contributed part of the ultimate molecule by virtue of a formaldehyde-derived methylene bridge connecting the amino nitrogen atom with a resin molecule; and with the further proviso that the resinous condensation product resulting from the process be heat-stable.

4. A process for breakingpetroleum emulsions of the water-in-oil type characterized by'subjecting the emulsion to the action of a demulsifier including the gluconic acid salts of :the basic products obtained-in turn in the process of condensing (a). an,oXyalkylation-susceptible, fusible, non-oxygenated organic solvent-soluble, water-insoluble, low stage phenol-aldehyde resin having an average molecular Weight corresponding to at least 3 and not over6 phenolic nuclei-per resin molecule; said resin being difunctional only in regard to methylol-forming reactivity; said resin being derived by reaction between a difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and reactive toward said phenol; said resin being formed in the substantial absence of trifunctional phenols; said phenol being of the formula in which R is an aliphatic hydrocarbon radical having at least 4 and not more than 24 carbon atoms and substituted in the 2,4,6 position; (b) a basic hydroxylated secondary monoamine having not more than 32 carbon atoms in any groupattached to the amino nitrogenatom, and (c) formaldehyde; said condensation reaction being conducted at a temperature sufficiently high to eliminate water and below the pyrolyticpoint of the reactants and resultants of reaction; with the proviso that the condensation reaction be conducted so as to produce a significant portion of the resultant in which each of the three-reactants have contributed part of the ultimate molecule by virtue of a formaldehyde-derived methylene bridge connecting the amino nitrogen atom with a resin molecule; with the further proviso that the molar ratio of reactants be approximately 1, 2 and 2 respectively; and with the final proviso that the resinous condensation product resulting from the process be heat-stable.

5. A process for breaking petroleum emulsions of the water-in-oil type characterized by subjecting the emulsion to the action of adernulsifier including thegluconicacid salts of the basic productsobtained in turn in the process of condensing (a) an oxyalkylation-susceptible, fusible, non-oxygenated organic solvent-soluble, water-insoluble, low-stage phenol-aldehyde resin having an average molecular weight corresponding to at least 3 and not over-6 phenolic nuclei resinmolecule; said resin being difunctional only in regard to methylol-forming reactivity;

said resin being derived by reaction between a difunctional monohydric phenol and an-aldehyde having not over 8 carbon atoms'and reactive toward said phenol; said resin being formed in the substantial absence of trifunctional phenols; said phenol being of the formula,

in which R is an aliphatic hydrocarbon radical having at least 4 and not more than 24 carbon atoms and substituted in the 2,4,6 position; (b) a basic hydroxylated secondary monoamine having not more than 32 carbon atoms in any group attached to the amino nitrogen atom, and (0) formaldehyde; said condensation reaction being conducted at a temperature sufiiciently high toeliminate water and below the pyrolytic point of the reactants and resultants of reaction, with the proviso that the condensation reaction be conducted so as to produce a significant portion of the resultant in which each of the three reactants have contributed part of the ultimate molecule by virtue of a formaldehyde-derived methylene bridge connecting the amino nitrogen atom with a resin molecule; with the added proviso that the molar ratio of reactants be approximately 1,2 and 2, respectively; with the further proviso that said procedure involve the use of a solvent;"

and with the final proviso that the resinous condensation product resulting from the process be heat-stable.

6. A process for breaking'petroleum emulsions of the,

in which R is an aliphatic hydrocarbon radical having at least 4 and not more than 24 carbon atoms and :sub-

stituted in the 2,4,6 position; (b) a basichydroxylated secondary monoamine having notvmore than 32 carbon atoms in any group attached tothe-amino nitrogenatom, and (c) formaldehyde; said condensation reactionbeing conducted at a temperature sufliciently'high toteliminate water and below the pyrolytic point ofthe reactants and resultants of reaction, with the proviso that the condensation reaction beconducted so as tovproduce. aisignificant portion of the resultant in which each of thethreereactantshave contributed part of the ultimate moleculebyvirtue of a formaldehyde-derived methylene bridge connecting the aminonitrogen atomvwith a-resin molecule; with the added proviso that the molar ratio of reactantsbe approximately 1,2 and 2, respectively; with the further proviso that said procedure involve theuse ,of asolvent; and with the final proviso that the resinousvcondensation product resulting from the process be; heatstable.

7. A process for breakingpetroleum emulsions of; the water-in-oil type characterized by subjecting the -;e mul- -sion to the action of a demulsifier including the gluconic acid salts of the basic products obtained, in .turn in the process of condensing (a) 1 an ,oxyethylanon-susceptible, fusible, non-oxygenated organic solvent-soluble, waterinsoluble, low-stages phenol-formaldehyde resin having an average molecular weight corresponding to at least 3. and not over 6 phenolic nuclei per resin molecule; said resin being difunctional only in regard to r nethylolforming reactivity; said resin being derived by reaction between a difunctional monohydric phenol and'formaldehyde; said resin'beingformedin-the substantialab- 17 sence of trifunctional phenols; said phenol being of the formula in which R is an aliphatic hydrocarbon radical having at least 4 and not more than 14 carbon atoms and substituted in the 2,4,6 position; (b) a basic hydroxylated secondary monoamine having not more than 32 carbon atoms in any group attached to the amino nitrogen atom, and (c) formaldehyde; said condensation reaction being conducted at a temperature sufliciently high to eliminate Water and below the pyrolytic point of the reactants and resultants of reaction, with the proviso that the condensation reaction be conducted so as to produce a significant portion of the resultant in which each of the three reactants have contributed part of the ultimate molecule by virtue of a formaldehyde-derived methylene bridge con necting the amino nitrogen atom with a resin molecule;

with the added proviso that the molar ratio of reactants be approximately 1, 2 and 2, respectively; with the further proviso that said procedure involve the use of a solvent; and with the final proviso that the resinous condensation product resulting from the process be heat-stable.

8. A process for breaking petroleum emulsions of the water-in-oil type characterized by subjecting the emulsion to the action of a demulsifier including the gluconic acid salts of the basic products obtained in turn in the process of condensing (a) an oxyethylation-susceptible, fusible, non-oxygenated organic solvent-soluble, water-insoluble, low-stage phenol-formaldehyde resin having an average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule; said resin being difunctional only in regard to methylol-forming reactivity; said resin being derived by reaction between a difunctional monohydric phenol and formaldehyde; said resin being formed in the substantial absence of trifunctional phenols; said phenol being of the formula in which R is an aliphatic hydrocarbon radical having at least 4 and not more than 14 carbon atoms and substituted in the 2,4,6 position; (b) a basic hydroxylated secondary monoamine having no more than 32 carbon atoms in any group attached to the amino nitrogen atom, and formaldehyde; said condensation reaction being conducted at a temperature above the boiling point of water and below 150 C., with the proviso that the condensation reaction be conducted so as to produce a significant portion of the resultant in which each of the three reactants have contributed part of the ultimate molecule by virtue of a formaldehyde-derived methylene bridge connecting the amino nitrogen atom with a resin molecule; with the added proviso that the molar ratio of reactants be approximately 1, 2 and 2, respectively; with the further proviso that said procedure involve the use of a solvent; and with the final proviso that the resinous condensation product resulting from the process be heatstable.

9. A process for breaking petroleum emulsions of the water-in-oil type characterized by subjecting the emulsion to the action of a demulsifier including the gluconic acid salts of the basic products obtained in turn in the process of condensing (a) an oxyethylation-susceptible, fusible, non-oxygenated organic solvent-soluble, water-insoluble, low-stage phenol-formaldehyde resin having an average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule; said resin being difunctional only in regard to methylol-forming reactivity; said resin being derived by reaction between a difunctional monohydric phenol and formaldehyde; said resin being formed in the substantial absence of trifunctional phenols; said phenol being of the formula" in which R is an aliphatic hydrocarbon radical having at least 4 and not more than 14 carbon atoms and substituted in the para position; (b) a basic hydroxylated secondary monoamine having not more than 32 carbon atoms in any group attached to the amino nitrogen atom, and (0) formaldehyde; said condensation reaction being conducted at a temperature above the boiling point of water and below C., with the proviso that the condensation reaction be conducted so as to produce a significant portion of the resultant in which each of the three reactants have contributed part of the ultimate molecule by virtue of a formaldehyde-derived methylene bridge connecting the amino nitrogen atom with a resin molecule; with the added proviso that the molar ratio of reactants be approximately 1, 2 and 2, respectively; with the further proviso that said procedure involve the use of a solvent; and with the final proviso that the resinous condensation product resulting from the process be heatstable.

10. The process of claim 1 with the proviso that the hydrophile properties of the glucoruc acid salt of the basic product in an equal weight of xylene are suflicient to produce an emulsion when said Xylene solution is shaken vigorously with l to 3 volumes of water.

11. The process of claim 2 with the proviso that the hydrophile properties of the gluconic acid salt of the basic product in an equal weight of xylene are suflicient to produce an emulsion when said xylene solution is shaken vigorously with 1 to 3 volumes of water.

12. The process of claim 3 with the proviso that the hydrophile properties of the gluconic acid salt of the basic product in an equal weight of xylene are suflicient to produce an emulsion when said Xylene solution is shaken vigorously with 1 to 3 volumes of water.

13. The process of claim 4 with the proviso that the hydrophile properties of the gluconic acid salt of the basic product in an equal weight of xylene are sufficient to produce an emulsion when said Xylene solution is shaken vigorously with 1 to 3 volumes of water.

14. The process of claim 5 with the proviso that the hydrophile properties of the gluconic acid salt of the basic b product in an equal weight of xylene are 'sufiicient to produce an emulsion when said xylene solution is shaken vigorously with 1 to 3 volumes of water.

15. The process of claim 6 with the proviso that the hydrophile properties of the gluconic acid salt of the basic product in an equal weight of xylene are sufficient to produce an emulsion when said xylene solution is shaken vigorously with 1 to 3 volumes of water.

16. The process of claim 7 with the proviso that the hydrophile properties of the gluconic acid salt of the basic product in an equal weight of xylene'are sufiicient to produce an emulsion When said Xylene solution is shaken vigorously with 1 to 3 volumes of water.

17. The process of claim 8 with the proviso that the hydrophile properties of the gluconic acid salt of the basic product in an equal weight of xylene are sufiicient to produce an emulsion when said xylene solution is shaken vigorously with 1 to 3 voluumes of Water.

18. The process of claim 9 with the proviso that the hydrophile properties of the gluconic acid salt of the basic product in an equal weight of xylene are suflicient to.

19 20 producaan emulsion. when said xylene solution is shaken 2,457,634 Bond et a1. Dec; 28, 1948;: vigorously with 1 to 3 volumes of Water. 2,535,380 Adams et a1 Dec. 26,1950;

: 2,545,692 Gleim Mar. 20, 1951 References Cited in thefile of this patent 2,542,001 De Groote et a1. Feb. 20, 1951 UNITED STATES PATENTS 2,568,739 Kirkpatrick et a1 Sept. 25, 1951 2,679,485 De Groote May 25, 1954 Bruson Feb. 18, 1936 

1. A PROCESS FOR BREAKING PETROLEUM EMULSIONS OF THE WATER-IN-OIL TYPE CHARACTERIZED BY SUBJECTING THE EMULSION TO THE ACTION OF A DEMULSIFIER INCLUDING THE GLUCONIC ACID SALTS OF THE BASIC PRODUCTS OBTAINED IN TURN IN THE PROCESS OF CONDENSING (A) AN OXYALKYLATION-SUSCEPTIBLE, FUSIBLE, NON-OXYGENATED ORGANIC SOLVENT-SOLUBLE, WATER-INSOLUBLE, LOW-STAGE, PHENOL-ALDEHYDE RESIN HAVING AN AVERAGE MOLECULAR WEIGHT CORRESPONDING TO AT LEAST 3 AND NOT OVER 6 PHENOLIC NUCLEI PER RESIN MOLECULE; SAID RESIN BEING DIFUNCTIONAL ONLY IN REGARD TO METHYLOL-FORMING REACTIVITY; SAID RESIN BEING DERIVED BY REACTION BETWEEN A DIFUNCTIONAL MONOHYDRIC PHENOL AND AN ALDEHYDE HAVING NOT OVER 8 CARBON ATOMS AND REACTIVE TOWARD SAID PHENOL; SAID RESIN BEING FORMED IN THE SUBSTANTIAL ABSENCE OF TRIFUNCTIONAL PHENOLS; SAID PHENOL BEING OF THE FORMULA 